PSG has now claimed the prestigious trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable win in the showdown featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
However, Marseille struck twice late to seize a surprise lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker grabbed a vital leveler in the dying seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for PSG to complete a convincing penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the last 13 years.
